Polynuclear chroma- and molybdacarborane containing M-H-B bridge bond and chromacarborane having sulfur-donor ligands were synthesized and characterized.
Dinuclear metallacarborane, $[(C_2B_9H_{10})Cr(μ-CO)_2(CO)(μ-H)CuCl]·(NMe_4)_2$ was prepared from the reaction system of $[closo-3,3,3-(CO)_3-3,1,2-Cr(C_2B_9H_{11})]·(NMe_4)_2/CuCl$ and $[closo-3,3,3-(CO)_3-3-Tl-3,1,2-Cr(C_2B_9H_{11})]·(NMe_4)/CuCl$. From the same reaction system, of which the cation is replaced as $NMe_4{^+}$, tetranuclear molybdacarborane $[Mo_2Cu_2(μ-CO)_4(CO)_2(μ_H)_2(C_2B_9H_{10})_2](PPN)_2 (PPN=N(PPh_3)_2)$ was prepared. Their crystal structures have been determined by single crystal X-ray diffraction.
The oxidative decarbonylation reactions of $[closo-3,3,3-(CO)_3-3,1,2-Cr(C_2B_9H_{11})]·(NMe_4)_2$ with tetraethylthiuramdisulfide and aldrithiol gave the oxidized products $[(C_2B_9H_{11})Cr(CO)_2(η^2-S_2CNEt_2)]·(NMe_4)$ and $[(C_2B_9H_{11})Cr(CO)_2(C_5H_4NS)]·(NMe_4)$ Their structures were established by spectroscopic analysis.
